EP1163051A1

EP1163051A1 - Catalyst comprising a metal complex of the viii subgroup based on a phosphine amidite ligand and its utilization for hydroformylation and hydrocyanation

Info

Publication number: EP1163051A1
Application number: EP00918832A
Authority: EP
Inventors: Wolfgang Ahlers; Heiko Maas; Michael Röper
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-03-24
Filing date: 2000-03-23
Publication date: 2001-12-19
Anticipated expiration: 2020-03-23
Also published as: JP2002539920A; DE19913352A1; US6852661B1; EP1163051B1; WO2000056451A1; DE50008598D1

Abstract

The invention relates to a catalyst comprising at least one metal complex of the VIII subgroup, which includes at least one monodentate, bidentate or polydentate phosphine amidite ligand of general formula I.1, I.2 and/or I.3, wherein A1, together with the phosphorus and the oxygen atoms to which it is bonded, represents a five to eight-membered heterocycle; X1 represents a five to eight-membered heterocycle having at least one nitrogen atom directly bonded to the phosphorous atom and B represents either a carbon-carbon single bond or a bivalent bridging group. The invention also relates to a method for hydroformylation and hydrocyanation of compounds containing at least one ethylinically unsaturated double bond in the presence of said catalyst.

Description

CATALYST COMPRISING A COMPLEX OF A METAL OF THE VIII. SUB-GROUP BASED ON A PHOSPHINAMIDITE LIGAND; ITS USE FOR HYDROFORMYLATION AND HYDROCYANATION

5 Description

The present invention relates to a catalyst which comprises at least one complex of a metal from subgroup VIII, which comprises at least one monodentate, bidentate or polydentate phosphine amidite ligand, and processes for hydroforming and hydrocyanating compounds which have at least one ethylenically unsaturated Contain double bond in the presence of such a catalyst.

15 Hydroformylation or oxo synthesis is an important large-scale process and is used to produce aldehydes from olefins, carbon monoxide and hydrogen. These aldehydes can optionally be hydrogenated in the same operation with hydrogen to the corresponding oxo alcohols. The reaction itself

20 is highly exothermic and generally takes place under elevated pressure and at elevated temperatures in the presence of catalysts. Co-, Rh-, Ir-, Ru-, Pd- or Pt-compounds or complexes are used as catalysts which are modified with N- or P-containing ligands to influence the activity and / or selectivity.

25 can be infected. The hydroformylation reaction leads to the formation of mixtures of isomeric aldehydes due to the possible CO addition to each of the two carbon atoms of a double bond. In addition, double bond isomerization can also occur. In these isomeric mixtures, the n-aldehyde is often

30 favored over the iso-aldehyde, with the aim of optimizing the hydroformylation catalysts to achieve greater n-selectivity due to the much greater technical importance of the n-aldehydes.

35 In Beller et al., Journal of Molecular Catalysis A, 104 (1995), pages 17-85, rhodium-containing, phosphine-modified catalysts for the hydroformylation of low-boiling olefins are described. A disadvantage of these catalysts is that they are only produced using organometallic reagents

40 can and the ligands used can only be produced in a complex and costly manner. In addition, these phosphine-modified catalysts make hydroformylation of internal, straight-chain and branched olefins and olefins with more than 7 carbon atoms very slow.

45 WO 95/30680 describes bidentate phosphine ligands in which the two phosphine groups are each bonded to an aryl radical and these two aryl radicals form a double-bridged, ortho-fused ring system, one of the two bridges consisting of an oxygen or a sulfur atom consists. Rhodium complexes based on these ligands are suitable as hydroformylation catalysts, a good n / iso ratio being achieved in the hydroformylation of terminal olefins. A disadvantage of these chelate phosphines is the high synthetic outlay for their preparation, so that technical processes based on such chelate phosphine catalysts are economically disadvantageous.

US Pat. No. 4,169,861 describes a process for the preparation of terminal aldehydes by hydroformylation of α-olefins in the presence of a rhodium hydroformylation catalyst based on a bidentate and a monodentate ligand. The bidentate ligand used is preferably 1, 1 'bis (diphenylphosphino) ferrocene. The monodentate ligand is preferably phosphine, such as diphenylethylphosphine. US-A-4,201,714 and US-A-4, 193,943 have a comparable disclosure content. The preparation of the bidentate phosphino-ferrocene ligands requires the use of organometallic reagents which are complex to produce, as a result of which hydroformylation processes using these catalysts are economically disadvantageous.

US-A-5, 312, 996 describes a process for the preparation of 1,6-hexanedial by hydroformylation of butadiene in the presence of hydrogen and carbon monoxide. Rhodium complexes with polyphosphite ligands are used as hydroformylation catalysts, in which the phosphorus and two of the oxygen atoms of the phosphite group are part of a 7-membered heterocycle.

JP-A 97/255 610 describes a process for the preparation of aldehydes by hydroformylation in the presence of rhodium catalysts which have a monodentate phosphonite ligand.

The catalytic hydrocyanation for the production of nitriles from olefins is also of great technical importance.

"Applied Homogeneous Catalysis with Organometalic Compounds", Vol. 1, VCH Weinheim, p. 465 ff. Generally describes the heterogeneous and homogeneously catalyzed addition of hydrogen cyanide to olefins. In particular, catalysts based on phosphine, phosphite and phosphonite complexes of nickel and palladium are used. CA Tolman et al. describe in Organometallics 1984, 3, p. 33 f. the catalytic hydrocyanation of olefins in the presence of nickel (0) -phosphite complexes with special consideration of the effects of Lewis acids on hydrogen cyanide addition.

In Advances in Catalysis, Volume 33, 1985, Academic Press Inc., pp. 1 f. the homogeneous nickel-catalyzed hydrocyanation of olefins is described in an overview. Nickel (0) complexes with phosphine and phosphite ligands are used as catalysts.

None of the aforementioned references describes hydroformylation catalysts or hydrocyanation catalysts based on mono-, bidentate or multidentate phosphinamidite ligands, the phosphorus and oxygen atoms of the phosphinamidite group being part of a 5- to 8-membered heterocycle.

The present invention has for its object to provide new catalysts based on complexes of a metal of subgroup VIII. These should preferably be suitable for hydroformylation or hydrocyanation and have good catalytic activity.

Surprisingly, catalysts based on complexes of a metal of subgroup VIII have now been found which comprise at least one monodentate, bidentate or polydentate phosphinamidite ligand, the phosphorus and oxygen atoms of the phosphinamidite group being part of a 5- to 8-membered heterocycle .

The present invention thus relates to a catalyst comprising at least one complex of a metal from subgroup VIII with at least one monodentate, bidentate or polydentate phosphinamidite ligand of the general formulas 1.1, 1.2 and / or 1.3

wherein A ¹ together with the phosphorus and the oxygen atom to which it is attached represents a 5- to 8-membered heterocycle which is optionally fused one, two or three times with cycloalkyl, aryl and / or hetaryl, where the fused groups can independently carry one, two or three substituents selected from alkyl, alkoxy, halogen, nitro, cyano, carboxyl and carboxylate,

A ² and A ³ independently of one another represent a heterocycle as defined for A ^{1 which} is substituted by B,

X ^{1 represents} a 5- to 8-membered heterocycle which has at least one nitrogen atom which is bonded directly to the phosphorus atom, and where the heterocycle optionally also has one or two heteroatoms selected from N, O and S. and / or wherein the heterocycle is optionally fused once, twice or three times with cycloalkyl, aryl and / or hetaryl, the heterocycle and / or the fused groups independently of one another each having one, two or three substituents which are selected from Alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, carboxylate, alkoxycarbonyl or EiE ² ', where E ¹ and E ^{2 can be the} same or different and for alkyl , Cycloalkyl or aryl,

X ² and X ³ independently of one another represent a heterocycle as defined for X ^{1 and} is substituted by B,

B represents either a carbon-carbon single bond or a divalent bridging group,

or salts and mixtures thereof.

In the context of the present invention, the term “alkyl” includes straight-chain and branched alkyl groups. These are preferably straight-chain or branched Ci-Cs-alkyl, more preferably Cx-C _ß- alkyl and particularly preferably Ci-C-alkyl groups. Examples of alkyl groups are in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl , 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-di- methylbutyl, 1, 3-dimethylbutyl, 2, 3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3, 3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1,2,2- Trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, octyl.

The cycloalkyl group is preferably a C ₅ -C cycloalkyl group, such as cyclopentyl, cyclohexyl or cycloheptyl.

If the cycloalkyl group is substituted, it preferably has 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy or halogen.

Aryl preferably represents phenyl, tolyl, xylyl, mesityl, naphthyl, anthracenyl, phenanthrenyl, naphthacenyl and in particular phenyl or naphthyl.

Substituted aryl radicals preferably have 1, 2, 3, 4 or 5, in particular 1, 2 or 3, substituents selected from alkyl, alkoxy, carboxyl, carboxylate, trifluoromethyl, nitro, cyano or halogen.

Hetaryl is preferably pyridyl, quinolinyl, acridinyl, pyridazinyl, pyrimidinyl or pyrazinyl.

Substituted hetaryl radicals preferably have 1, 2 or 3 substituents selected from alkyl, alkoxy, trifluoromethyl or halogen.

The above statements on alkyl, cycloalkyl and aryl radicals apply accordingly to alkoxy, cycloalkyloxy and aryloxy radicals.

The NE ^X E ² radicals are preferably N, N-dimethyl, N, N-diethyl, N, N-dipropyl, N, N-diisopropyl, N, N-di-n-butyl, N, N-di-t . -butyl, N, N-dicyclohexyl or N, N-diphenyl.

Halogen represents fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine. ^~

In the context of this invention, carboxylate preferably represents a derivative of a carboxylic acid function, in particular a metal carboxylate, a carboxylic acid ester function or a carboxylic acid amide function, particularly preferably a carboxylic acid ester function. These include, for example, the esters with -CC alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol. In the formulas 1.1 and 1.2, the radicals A ¹ and in the formula 1.3 the radicals A ² and A ^{3, in} each case together with the phosphorus and oxygen atoms of the phosphinamidite group to which they are bonded, preferably represent a 5- to 8- membered heterocycle, which can optionally be fused once or twice with aryl and / or hetaryl.

The fused aryls of the radicals A ¹ »A ² and / or A ³ are preferably benzene or naphthalene, in particular benzene.

The fused aryls and / or hetaryls of the radicals A ¹ »A ² and / or A ³ are preferably unsubstituted or each have 1, 2 or 3, in particular 1 or 2, substituents which are alkyl, alkoxy, trifluoromethyl, halogen, nitro, Cyano, carboxyl and carboxylate are selected.

A ¹ preferably represents a 2,2'-biphenylene, 2, 2 '-binaphthylene or 2, 3-xylylene radical, the 1, 2 or 3 substituents selected from alkyl, alkoxy, trifluoromethyl, carboxylate or halogen, can carry. Alkyl is preferably C 1 -C 4 -alkyl and in particular t-butyl. Alkoxy is preferably C 1 -C ₄ alkoxy and in particular methoxy. Halogen is especially fluorine, chlorine or bromine.

A ² and A ³ are preferably a 2, 2'-biphenylene residue. These radicals A ² and A ³ preferably have the bridging group B in the para position to the phosphorus atom or to the oxygen atom of the phosphinamidite group.

In formulas 1.1 and 1.3, the radicals X ¹ and in the formula 1.2 the radicals X ² and X ³ each preferably represent a 5- or 6-membered heterocycle which has at least one nitrogen atom which is attached directly to the phosphorus atom with the formation of a Phosphinamiditgruppe is bound. Preferred radicals X ¹ , X ² and / or X ³ may additionally have one or two heteroatoms selected from N, 0 and S. The additional heteroatoms are preferably nitrogen atoms. Preferred radicals X ¹ , X ² and / or X ³ are additionally fused once or twice with aryl and / or hetaryl. Non-fused heterocycles are preferably unsubstituted or have one, two or three substituents which are selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, carboxylate, alkoxycarbonyl or NE ¹ E ² »can bear, where E ¹ and E ^{2 may be the} same or different and stand for alkyl, cycloalkyl or aryl. In the case of singly fused radicals X ¹ , X ² and / or X ³ , the heterocycle is preferred unsubstituted or has one of the aforementioned substituents on the heterocycle. In the case of single and double fused radicals X ¹ , X ² and / or X ³ , the fused rings preferably each have 1, 2 or 3, in particular 1 or 2, of the aforementioned substituents, independently of one another.

The radicals X ¹ , X ² and X ³ are preferably selected from aromatic heterocycles.

If the radicals X ¹ , X ² and / or X ^{3 have} fused aryls, they are preferably benzene or naphthalene, in particular benzene.

The radicals X ¹ 'X ² and X ³ are preferably selected independently of one another from 1-pyrrolyl, 1-pyrazolyl, 1-imidazolyl, 1-triazolyl, 1-indyl, 1-indazolyl, 7-purinyl, 2-isoindyl, and 9-carbazolyl, which optionally carry one, two or three of the aforementioned substituents.

The radicals X ² and X ³ preferably represent a 1-pyrrolyl radical which the bridging group B in the 2 position or in the 3 position, in particular in the 2 position. having. In addition, this can carry one, two or three of the aforementioned substituents in the 3-, 4- and / or 5-position.

The bridging group B preferably represents a carbon-carbon single bond or a divalent bridging group with 1 to 15 atoms in the chain between the flanking bonds.

B preferably represents a bridging group of the general formulas -D-, - (CO) -D- (CO) - or - (CO) - (CO) -, in which

D represents a Ci to C o-alkylene bridge, the one, two, three or four double bonds and / or one, two, three or four substituents which are selected from alkyl, alkoxy, halogen, nitro, cyano, carboxyl, carboxylate , Cycloalkyl and aryl, where the aryl substituent can additionally carry one, two or three substituents which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, and / or the alkylene bridge D can be interrupted by one, two or three non-adjacent, optionally substituted heteroatoms, and / or the alkylene bridge D can be fused one, two or three times with aryl and / or hetaryl, the fused aryl and hetaryl groups each having one or two or three substituents which are selected from alkyl, cycloalkyl, aryl, alkoxy, Cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE ¹ E ² , can be worn, where E ¹ and E ^{2 can be the} same or different and stand for alkyl, cycloalkyl or aryl.

The radical D preferably represents a C 1 -C ₈ -alkylene bridge which, depending on the number of carbon atoms, is fused 1-, 2- or 3-fold with aryl and / or the 1, 2, 3 or 4 substituents which are selected under alkyl, cycloalkyl and optionally substituted aryl, and / or which may additionally be interrupted by 1, 2 or 3 optionally substituted heteroatoms.

The fused aryls of the radicals D are preferably benzene or naphthalene, in particular benzene. Fused benzene rings are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2, substituents which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, carboxyl, alkoxycarbonyl and cyano. Fused naphthalenes are preferably unsubstituted or have 1, 2 or 3, in particular 1 or 2, of the substituents previously mentioned for the fused benzene rings in the non-fused ring and / or in the fused ring. This is then preferably alkyl or alkoxycarbonyl. In the case of the substituents of the fused aryls, alkyl preferably represents C 1 -C ₄ -alkyl and in particular methyl, isopropyl and tert-butyl. Alkoxy is preferably Ci to C ₄ alkoxy and in particular methoxy. Alkoxycarbonyl is preferably Ci to C ₄ alkoxycarbonyl. Halogen is especially fluorine and chlorine.

If the alkylene bridge of the radical D is interrupted by 1, 2 or 3, optionally substituted heteroatoms, these are preferably selected from O, S or NR ¹⁰ , where R ^{10 is} alkyl, cycloalkyl or aryl.

If the alkylene bridge of the radical D is substituted, it has 1, 2, 3 or 4 substituents, which is / are preferably selected from alkyl, cycloalkyl and aryl, the aryl substituent additionally 1, 2 or 3 substituents, which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl and cyano. The substituents on the alkylene bridge D are preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, phenyl, p- (C 1 -C 8 -alkyl) phenyl, preferably p- Methylphenyl, p- (Cχ- to C ₄ -alkoxy) phenyl, preferably p-methoxyphenyl, p-halophenyl, preferably p-chlorophenyl and p-trifluoromethylphenyl. According to a preferred embodiment, D represents a non-fused Cχ to C alkylene bridge which is substituted as described above and / or interrupted by optionally substituted heteroatoms. In particular, the radical D represents a Cχ ~ to C ₅ alkylene bridge which has 1, 2, 3 or 4 substituents which are selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and phenyl.

According to a further preferred embodiment, D represents a radical of the formula II.1, II.2, II.3, II.4 or II.5

wherein

Y stands for 0, S, NR ⁹ , where

R ^{9 represents} alkyl, cycloalkyl or aryl,

or Y represents a Cχ ~ to C ₃ alkylene bridge which may have a double bond and / or an alkyl, cycloalkyl or aryl substituent, the aryl substituent being one, two or three substituents which are selected from alkyl, alkoxy, Halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano,

or Y represents a C ₂ -C ₃ -alkylene bridge which is interrupted by 0, S or NR ⁹ ,

R ¹ , R ² 'R ³ _' R ⁴ 'R ⁵ ' R ⁶ _' R ⁷ and R ⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano. In particular, the phosphinamidite ligand is selected from ligands of the formulas purple to uli

(purple) (iiib) (IIIC)

(iiid) (Ille)

(Ulf)

(Illg)

(There)

(Uli)

wherein

R ⁹ and R ¹⁰ independently of one another represent hydrogen, methyl, ethyl or trifluoromethyl, R ^{11 represents} hydrogen or COOC ₂ H ₅ ,

B represents CH ₂ , C (CH ₃ ) ₂ , (CO) - (CO) or (CO) -D- (CO),

where B in the formulas Illg, Illh and Uli each in the

0.0, m, m or p, p positions to the phosphorus atoms and

D represents a ci to cio alkylene bridge which has one, two, three or four double bonds and / or which can be substituted as described above and / or interrupted by optionally substituted heteroatoms and / or fused with aryl and / or hetaryl.

The catalysts of the invention can have one or more of the phosphinamidite ligands of the formulas 1.1, 1.2 and 1.3. In addition to the ligands of the general formulas 1.1, 1.2 and 1.3 described above, they can also have at least one further ligand which is selected from halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, Nitriles, N-containing heterocycles, aromatics and heteroaromatics, ethers, PF ₃ and monodentate, bidentate and multidentate phosphine, phosphinite, phosphonite and phosphite ligands. These further ligands can also be monodentate, bidentate or multidentate and coordinate on the metal atom of the catalyst complex. Suitable other phosphorus-containing ligands are e.g. B. usual phosphine, phosphonite, and phosphite ligands.

To prepare the phosphinamidite ligands of the formula 1.1 used according to the invention, z. B. a hydroxyl group-containing compound of formula IV with a phosphorus trihalide, preferably PCI ₃ , to a compound of formula V and this then with a compound HX ¹ , which has at least one secondary amino group, according to the following scheme

IV V (1.1)

implement, wherein A ¹ and X ^{1 have} the meanings given above. Examples of suitable compounds of formula IV are e.g. B. biphenyl-2-ol, binaphthyl-2-ol, 1, 1'-biphenyl-4-phenyl-2-ol, 1, l'-biphenyl-3,3 ', 5, 5' -tetra- t-butyl-2-ol, 1, 1'-biphenyl 3,3'-di-t-amyl-5, 5 '-dimethoxy-2-ol, 1,1'-biphenyl-3, 3' -di-t-butyl-5, 5'-dimethoxy-2 -ol, 1,1'-biphenyl-3, 3 '-di-t-butyl-2-ol, 1,1'-biphenyl-3, 3'-di-t-butyl-6,6'-dimethyl- 2-ol, 1,1'-biphenyl-3, 3 ', 5, 5' -tetra-t-butyl-6, 6'-dimethyl-2-ol, 1,1'-biphenyl-3, 3 '- di-t-butyl-5,5'-di-t-butoxy-2-ol, 1, 1 '-biphenyl-3, 3' -di-t-he-xyl-5, 5 '-dimethoxy-2- ol, 1,1'-biphenyl-3-t-butyl-5, 5'-di-ethoxy-2-ol, 1, 1 '-biphenyl-3,3'- di [2- (1, 3- dioxacyclohexane)] - 5, 5 '-dimethoxy-2-ol, 1, 1' -biphenyl-3, 3 '-diformyl-5, 5' -dimethoxy-2-ol and 1, 1 '-biphenanthrene-2 -ol, especially biphenyl-2-ol and binaphthyl-2-ol.

Examples of suitable compounds HX ¹ are, for example, pyrrole, pyrazole, imidazole, 1-triazole, indole, indazole, purine, isoindole and carbazole.

To prepare the phosphinamidite ligands of the formula 1.2 used according to the invention, z. B. two moles of at least one compound of general formula V with one mole of a compound HX ² -BX ³ H, wherein X ² , X ³ and B have the meanings given above and which has at least two secondary amino groups, according to the following scheme

implement. When only one compound of the type of formula V is used, phosphinamidite ligands with two identical phosphine amiditrests are obtained. However, if desired ^~ are bridged, two different compounds of the formula V with a compound HX ² -BX ³ H.

Suitable amines of the formula HX ² -BX ³ H are, for example, customary alkylene-bridged bispyrroles and diacyl-bridged bispyrroles known to the person skilled in the art.

A process for the preparation of these ligands is described in

DE-A-195 21 340, US 5,739,372 and in Phosphorus and Sulfur, 1987, Vol. 31, p. 71 ff. For the construction of 6H-di benz [c, e] [1,2 Joxaphosphorin ring systems. Full reference is made here to these documents.

To prepare the phosphinamidite ligands of the formula 1.3 used according to the invention, z. B. a compound of formula VI, which has two hydroxyl groups with a phosphorus trihalide, preferably PC1 ₃ , to a compound of formula VII and then with at least one compound HX ¹ , as previously described in the preparation of the phosphinamidite ligands of formula 1.1 ben, according to the following scheme

implement, wherein A ² , A ³ and X ^{1 have} the meanings given above. If desired, two different compounds HX ^{1 can also be used} to prepare the compounds of the formula 1.3.

If desired, the compounds of the formulas V and VII can be isolated and isolated by known methods, such as, for. B. distillation, crystallization, chromatography u. Ä. are cleaned.

The reaction of compounds of the formula IV to compounds of the formula V and of compounds of the formula VI to compounds of the formula VII generally takes place at an elevated temperature in a range from about 40 to about 200 ° C., the reaction also being carried out with a successive increase in temperature can be. In addition, at the start of the reaction or after a certain reaction time, a Lewis acid, such as. As zinc chloride or aluminum chloride, can be added as a catalyst. The further reaction of compounds of the formulas V and VII to the phosphinamidite ligands of the formulas 1.1, 1.2 and 1.3 used according to the invention is generally carried out in the presence of a base, for. B. an aliphatic amine, such as diethylamine, dipropylamine, dibutylamine, trimethylamine, tripropylamine and preferably triethylamine or pyridine. The preparation can also be carried out by deprotonation of the nitrogen heterocycle with a base and subsequent reaction with a compound of the formula V or VII. For de- Bases suitable for protonation are, for example, alkali hydrides, preferably sodium hydride and potassium hydride, alkali amides, preferably sodium amide, lithium diisopropylamide, n-butyllithium etc.

Advantageously, the phosphinamidite ligands used according to the invention can be prepared without using magnesium or lithium-organic compounds. The simple reaction sequence allows the ligands to be varied widely. The presentation is thus efficient and economical from easily accessible starting materials.

In general, under hydroformylation conditions, catalytically active species of the general formula H _x M _y (C0) _z L _{q are} formed from the catalysts or catalyst precursors used in each case, where M is a metal from subgroup VIII, L is a phosphinamidite ligand and q, x, y, z are integers, depending on the valency and type of the metal and the binding nature of the ligand L. Preferably, z and q are independently at least 1, such as. B. 1, 2 or 3. The sum of z and q is preferably from 2 to 5. The complexes can, if desired, additionally have at least one of the further ligands described above.

The metal M is preferably cobalt, ruthenium, rhodium, nickel, palladium, platinum, osmium or iridium and in particular cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum.

According to a preferred embodiment, the hydroformylation catalysts are prepared in situ in the reactor used for the hydroformylation reaction. If desired, however, the catalysts of the invention can also be prepared separately and isolated by customary processes. For the in-situ production of the catalysts according to the invention, e.g. implement at least one phosphinamidite ligand of the general formulas 1.1, 1.2 and / or 1.3, a compound or a complex of a metal from subgroup VIII, optionally at least one further additional ligand and optionally an activating agent in an inert solvent under the hydroformylation conditions.

Suitable rhodium compounds or complexes are e.g. B. rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II ) - or rhodium (III) carboxylate, rhodium (II) - and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) - acid, trisammonium hexachlororhodate (III) etc. Rhodium complexes, such as rhodium biscarbonylacetylacetonate, acetyl acetonatobisethylene rhodium (I) etc. are also suitable. Rhodium biscarbonylacetylacetonate or rhodium acetate are preferably used.

Ruthenium salts or compounds are also suitable. Suitable ruthenium salts are, for example, ruthenium (III) chloride, ruthenium (IV) -, ruthenium (VI) - or ruthenium (VIII) oxide, alkali metal salts of ruthenium oxygen acids such as K ₂ Ru0 ₄ or KRu0 ₄ or complex compounds, such as, for. B. RuHCl (CO) (PPh ₃ ) ₃ . The metal carbonyls of ruthenium, such as trisruthenium dodecacarbonyl or hexaruthenium octadecacarbonyl, or mixed forms in which CO is partially replaced by ligands of the formula PR ₃ , such as Ru (CO) ₃ (PPh ₃ ) ₂ , can also be used in the process according to the invention.

Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carboxylates, such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate, and cobalt caprolactamate -Complex. Here too, the carbonyl complexes of cobalt such as dicobalt octacarbonyl, tetracobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can be used.

The above-mentioned and other suitable compounds of cobalt, rhodium, ruthenium and iridium are known in principle and are adequately described in the literature, or they can be prepared by the skilled worker analogously to the already known compounds.

Suitable activating agents are e.g. B. Brönsted acids, Lewis acids, such as. B. BF ₃ , AICI ₃ , ZnCl ₂ , and Lewis bases.

The solvents used are preferably the aldehydes which are formed in the hydroformylation of the respective olefins, and also their higher-boiling secondary reaction products, for. B. the products of aldol condensation. Likewise suitable solvents are aromatics, such as toluene and xylenes, hydrocarbons or mixtures of hydrocarbons, also for diluting the above-mentioned aldehydes and the secondary products of the aldehydes. With sufficiently hydrophilized ligands, water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ketones such as acetone and methyl ethyl ketone etc. can also be used. The molar ratio of phosphine idite ligand to metal VIII. Sub-group is generally in the range of about 1: 1 to 1,000: 1.

The invention further provides a process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of at least one of the hydroformylation catalysts according to the invention.

In principle, all compounds which contain one or more ethylenically unsaturated double bonds are suitable as substrates for the hydroformylation process according to the invention. These include e.g. B. olefins, such as α-olefins, internal straight-chain and internal branched olefins. Suitable α-olefins are e.g. B. ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene etc.

Suitable straight-chain internal olefins are preferably C ₄ - to C ₂ o-olefins such as 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 4 -Octen etc.

Suitable branched, internal olefins are preferably C to C ₂₀ olefins, such as 2-methyl-2-butene, 2-methyl-2-pentene, 3-methyl-2-pentene, branched, internal heptene mixtures, branched , internal octene mixtures, branched, internal non-mixtures, branched, internal decene mixtures, branched, internal undecene mixtures, branched, internal dodecene mixtures etc.

Suitable olefins to be hydroformylated are furthermore C ₅ -C 6 -cycloalkenes, such as cyclopentene, cyclohexene, cycloheptene, cyclooctene and their derivatives, such as, for. B. their Ci to C ₂ o-alkyl derivatives with 1 to 5 alkyl substituents. Suitable olefins to be hydroformylated are also vinyl aromatics, such as styrene, α-methylstyrene, 4-isobutylstyrene etc. Suitable olefins to be hydroformylated are furthermore α, β-ethylenically unsaturated mono- and / or dicarboxylic acids, their esters, half-esters and amides, such as acrylic acid , Methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, 3-pentenoic acid methyl ester, 4-pentenoic acid methyl ester, oleic acid methyl ester, acrylic acid methyl ester, methacrylic acid methyl ester, unsaturated nitriles, such as 3-pentenenitrile, 4-pentenenitrile vinyl, acrylate, such as acrylonitrile Vinyl ethyl ether, vinyl propyl ether etc., Ci to C ₂₀ alkenols, alkylene diols and alkadienols, such as 2, 7-octadienol-1. Suitable substrates are further di- or polyenes with isolated or conjugated double bonds. These include e.g. B. 1,3-butadiene, 1,4-pentadiene, 1, 5-hexadiene, 1,6-heptadiene, 1, 7-octadiene, vinylcyclohexene, dicyclopentadiene, 1,5,9-cyclooctatriene and butadiene homo- and copolymers.

A process is preferred which is characterized in that the hydroformylation catalyst is prepared in situ, using at least one phosphinamide ligand according to the invention, a compound or a complex of a metal from subgroup VIII and, if appropriate, an activating agent in an inert solvent under the hydroformylation conditions to react tion brings.

The hydroformylation reaction can be carried out continuously, semi-continuously or batchwise.

Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, p. 743 ff.

Suitable pressure-resistant reactors are also known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Vol. 1, 3rd Edition, 1951, pp. 769 ff. In general, an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.

The composition of the synthesis gas of carbon monoxide and hydrogen used in the process according to the invention can vary within wide ranges. The molar ratio of carbon monoxide and hydrogen is usually about 5:95 to 70:30, preferably about 40:60 to 60:40. A molar ratio of carbon monoxide and hydrogen in the range of approximately 1: 1 is particularly preferably used.

The temperature in the hydroformylation reaction is generally in the range from about 20 to 180 ° C., preferably about 50 to 150 ° C. The reaction is usually carried out at the partial pressure of the reaction gas at the selected reaction temperature. In general, the pressure is in a range from about 1 to 700 bar, preferably 1 to 600 bar, in particular 1 to 300 bar. The reaction pressure can be varied depending on the activity of the hydroformylation catalyst according to the invention used. In general, the catalysts according to the invention based on phosphinamidite ligands allow reaction in a range of low pressures, such as in the range from 1 to 100 bar. The hydroformylation catalysts according to the invention can be separated from the discharge of the hydroformylation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydroformylation.

The catalysts according to the invention advantageously have a high activity, so that the corresponding aldehydes are generally obtained in good yields. In the hydroformylation of α-olefins and of internal linear olefins, they also show a very low selectivity for the hydrogenation product of the olefin used.

The catalysts according to the invention described above, which comprise chiral phosphinamidite ligands, are suitable for enantioselective hydroformylation.

Another object of the invention is the use of catalysts, comprising one of the phosphinamidite ligands described above, for the hydroformylation of compounds having at least one ethylenically unsaturated double bond.

Another area of use for the catalysts according to the invention is the hydrocyanation of olefins. The hydrocyanation catalysts according to the invention also comprise complexes of a metal from subgroup VIII, in particular cobalt, nickel, ruthenium, rhodium, palladium, platinum, preferably nickel, palladium and platinum and all particularly preferably nickel. As a rule, the metal is zero-valued in the metal complex according to the invention. The metal complexes can be prepared as previously described for use as hydroformylation catalysts. The same applies to the in situ production of the hydrocyanation catalysts according to the invention.

A nickel complex suitable for the preparation of a hydrocyanation catalyst is e.g. Bis (1,5-cyclooctadiene) nickel (0).

If appropriate, the hydrocyanation catalysts can be prepared in situ, analogously to the process described for the hydroformylation catalysts.

The invention therefore furthermore relates to a process for the preparation of nitriles by catalytic hydrocyanation, which is characterized in that the hydrocyanation takes place in the presence of at least one of the catalysts according to the invention described above. Suitable olefins for hydrocyanation are generally the olefins previously mentioned as starting materials for hydroformylation. A special embodiment of the According to the process relates to the preparation of mixtures of mono-olefinic C ₅ mononitriles with non-conjugated C = C and C≡N bonds by catalytic hydrocyanation of 1,3-butadiene or 1,3-butadiene-containing hydrocarbon mixtures and the isomerization / Further reaction to saturated C-dinitriles, preferably adiponitrile in the presence of at least one catalyst according to the invention. When using hydrocarbon mixtures for the production of monoolefinic Cs-mononitriles by the process according to the invention, a hydrocarbon mixture is preferably used which has a 1,3-butadiene content of at least 10% by volume, preferably at least 25% by volume, in particular at least 40% Vol .-% has.

1,3-butadiene-containing hydrocarbon mixtures are available on an industrial scale. So z. B. in the work-up of petroleum by steam cracking of naphtha a C-cut hydrocarbon mixture with a high total olefin content, with about 40% on 1,3-butadiene and the rest on mono-olefins and polyunsaturated hydrocarbons and Al- kane is dropped. These streams always contain small amounts of generally up to 5% of alkynes, 1,2-dienes and vinyl acetylene.

Pure 1,3-butadiene can e.g. B. be isolated by extractive distillation from commercially available hydrocarbon mixtures.

The catalysts according to the invention can advantageously be used for the hydrocyanation of such olefin-containing, in particular 1,3-butadiene-containing, hydrocarbon mixtures, as a rule also without prior purification of the hydrocarbon mixture by distillation. Possible contained, the effectiveness of the catalysts impairing olefins, such as. B. alkynes or cumulenes, can optionally be removed from the hydrocarbon mixture by selective hydrogenation before the hydrocyanation. Suitable processes for selective hydrogenation are known to the person skilled in the art.

The hydrocyanation according to the invention can be carried out continuously, semi-continuously or batchwise. Suitable reactors for the continuous reaction are known to the person skilled in the art and are described, for. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd edition, 1951, p. 743 ff. A stirred tank cascade or a tubular reactor is preferably used for the continuous variant of the process according to the invention. Suitable, optionally pressure-resistant reactors for semi-continuous or continuous execution are known to the person skilled in the art. knows and z. B. in Ullmann's Encyclopedia of Industrial Chemistry, Volume 1, 3rd Edition, 1951, pp 769 ff. In general, an autoclave is used for the method according to the invention, which can, if desired, be provided with a stirring device and an inner lining.

The hydrocyanation catalysts according to the invention can be separated from the discharge of the hydrocyanation reaction by customary processes known to the person skilled in the art and can generally be used again for the hydrocyanation.

The invention is illustrated by the following, non-limiting examples.

Examples

If desired, the ligands described below can be further purified by customary purification processes known to those skilled in the art, such as crystallization and distillation.

A) Preparation of the ligands purple to IIIc

Example 1: Preparation of purple ligand

206 g (1.5 mol) of phosphorus trichloride and 204 g (1.2 mol) of biphenyl-2-ol are slowly heated to 50 ° C. with stirring in an argon atmosphere and further to 140 ° C. within 8 hours. The solution turns yellow when there is a strong evolution of hydrogen chloride. After cooling to 120 ° C., a catalytic amount of zinc chloride (1.2 g; 17 mmol) is added and the mixture is heated at 140 ° C. for 24 hours. In the subsequent distillation, the reaction product 6-chloro (6H) -dibenz [c, e] [1.2 joxaphosphorine at a boiling point of 132 ° C. (0.2 mbar) passes over.

Yield: 194.8 g (69%) white crystals; ³¹ P NMR Spectrum: δ (ppm) 134.5.

Further processes for the preparation of 6-chloro (6H) -dibenz [c, e] [1,2] oxaphosphorin are described in DE-A-20 34 887 and EP-A-0 582 957.

2.9 g of potassium hydride (35% suspension in mineral oil; 25 mmol) are placed in 80 ml of tetrahydrofuran under an argon atmosphere. Then 1.75 g (26 mmol) of pyrrole are slowly added dropwise, the temperature rising to about 33 ° C. After the evolution of hydrogen has ended, 6 g (26 mmol) of 6-chloro (6H) di benz [c, e] [1,2 joxaphosphorin as a solution in 40 ml of tetrahydrofuran and then stirred at room temperature for 12 h. The mixture is evaporated to dryness, taken up in toluene and filtered through a 2 cm diatomaceous earth column. After the solvent has been evaporated off, the ligand is obtained in purple as a white solid.

15

(purple)

20 Yield: 3.3 g (50%) of white crystals; ³¹ P NMR spectrum (CDC1 ₃ ): δ (ppm) 77.2 ¹ H NMR spectrum: corresponds to the proposed structure

Alternatively, 9.7 g (36.6 25 mmol) of 6-chloro (6H) -dibenz [c, e] [1.2 ioxaphosphorine as a solution in 80 ml of toluene can be initially introduced to prepare purple ligand, then 4.9 Add g (73.2 mmol) pyrrole and then slowly add 7.6 g (75 mmol) triethylamine at room temperature, whereby a mist of triethylamine hydrochloride forms immediately. The mixture is stirred at 70 ° C. for 6 h and then at room temperature for 12 h 30. After filtration, the resulting filtrate is evaporated to dryness, the residue is taken up in methyl tert-butyl ether and then precipitated by cooling to -30 ° C. Yield: 6.7 g (72%); 35 ³¹ P-NMR spectrum (CDC1 ₃ ): as above ⁱ H-NMR spectrum: corresponds to the proposed structure

Example 2:

Production of ligand illb

40

Analogous to the synthesis instructions given in Example 1, the ligand Illb is prepared by reacting 6-chloro (6H) -dibenz [c, e] [1,2 joxaphosphorin with indole and triethylamine as the base. The product obtained is cleaned with water

45 water washed and recrystallized from acetonitrile.

10

(Illb)

15 ³¹ P NMR spectrum (CDC1 ₃ ): δ (pp) 66.7

¹ H-NMR spectrum: corresponds to the proposed structure

Example 3:

Preparation of Ligand IIIc

20th

Analogously to the synthesis instructions given in Example 1, the ligand IIIc is prepared by reacting 6-chloro (6H) -dibenz [c, e] [1,] oxaphosphorin with carbazole and triethylamine as the base.

25

35 (IIIC)

³¹ P-NMR spectrum (CDC1 ₃ ): δ (ppm) 81.4 40 ^ -H-NMR spectrum: corresponds to the proposed structure

B) Hydroformylations

Example 4: 45 Hydroformylation of 1-octene 123 mg of rhodium biscarbonyl acetylacetonate, 680 mg of ligand lilac, 22.5 g of 1-octene and 25 ml of Texanol® (solvent based on 2,2,4-trimethylpentane-l, 3-diolmonoisobutyrate) were placed in a 300 ml steel autoclave with a gassing stirrer under an argon protective gas ) at 100 ° C with a synthesis gas mixture CO / H ₂ (1: 1) at 40 bar (108 ppm Rh; ligand / metal ratio = 54). After a reaction time of 4 hours, the autoclave was let down and emptied. The mixture was analyzed by internal standard gas chromatography (GC). The conversion was 100%, the selectivity for nonanal isomers was 96% and the n content was 80%.

Example 5: Hydroformylation of 1-octene

Analogously to Example 4 were nat 134 mg Rhodiumbiscarbonylacetylaceto-, 310 mg of ligand IIIb, 22.5 g of 1-octene and 25 ml of Texanol ^® used for the hydroformylation (118 ppm Rh; ligand / metal ratio = 19). The conversion was 99%, the selectivity for nonanal isomers 88% and the n content 68%.

Example 6: Hydroformylation of 1-octene

Analogously to Example 4, 12.4 mg Tonat Rhodiumbiscarbonylacetylace-, 480 mg ligand IIIc, 22.5 g of 1-octene and 22.5 g of Texanol ^® used for the hydroformylation (109 ppm Rh; ligand / metal ratio = 45). The conversion was 99%, the selectivity for nonanal isomers was 82% and the n content was 51%.

Example 7:

Hydroformylation of 3-pentenenitrile

According to the general procedure of Example 4, 6.2 mg of rhodium biscarbonylacetylacetonate, 322 mg of ligand purple, 10 g of 3-pentenenitrile and 15 g of xylene at a temperature of 110 ° C., a pressure of 80 bar and a reaction time of 4 h became Hydroformylation used (100 ppm Rh; ligand / metal ratio = 50). The conversion was 69% and the selectivities for 3-formylvaleronitrile 65%, for 4-formylvaleronitrile 24% and for 5-formylvaleronitrile 4%.

Example 8:

Hydroformylation of 3-pentenenitrile 6.2 mg of rhodium biscarbonylacetylacetonate, 382 mg of ligand Illb, 10 g of 3-pentenenitrile and 15 g of xylene at a temperature of 110 ° C., a pressure of 70 bar and a reaction time of 4 hours were added in accordance with the general instructions of Example 4 Hydroformylation used (100 ppm Rh; ligand / metal ratio = 50). The conversion was 99% and the selectivities for 3-formylvaleronitrile 59%, for 4-formylvaleronitrile 30% and for 5-formylvaleronitrile 9%.

Example 9:

Hydroformylation of 3-pentenenitrile

According to the general procedure of Example 4, 6.2 mg of rhodium biscarbonylacetylacetonate, 443 mg of ligand IIIc, 10 g of 3-pentenenitrile and 15 g of xylene at a temperature of 110 ° C., a pressure of 70 bar and a reaction time of 4 h Hydroformylation used (100 ppm Rh; ligand / metal ratio = 50). The conversion was 80% and the selectivities for 3-formylvaleronitrile 41%, for 4-formylvaleronitrile 38% and for 5-formylvaleronitrile 18%.

Example 10

Hydroformylation of octene-N

According to the general procedure of Example 4, 126 mg of rhodium biscarbonyl acetylacetonate, 270 mg of ligand purple, 22.5 g of octene-N and 22.5 g of Texanol® were at a temperature of 130 ° C, a pressure of 60 bar and a reaction time of 6 h used for hydroformylation (111 ppm Rh; ligand / metal ratio = 20). The conversion was 59% and the selectivity for nonanal isomers 85% and 11% for nonanol isomers.

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Claims

claims

1. A catalyst comprising at least one complex of a metal of subgroup VIII with at least one monodentate, bidentate or multidentate phosphinamidite ligand of the general formula 1.1, 1.

2 and / or 1.3

wherein

A ¹ together with the phosphorus and the oxygen atom to which it is attached represents a 5- to 8-membered heterocycle which is optionally fused one, two or three times with cycloalkyl, aryl and / or hetaryl, where the fused groups can independently carry one, two or three substituents selected from alkyl, alkoxy, halogen, nitro, cyano, carboxyl and carboxylate,

X ^{1 represents} a 5- to 8-membered heterocycle which has at least one nitrogen atom which is bonded directly to the phosphorus atom, and where the heterocycle can optionally have one or two heteroatoms selected from N, 0 and S. and / or wherein the heterocycle is optionally fused once, twice or three times with cycloalkyl, aryl and / or hetaryl, the heterocycle and / or the fused groups independently of one another each having one, two or three substituents which are selected from Alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, carboxylate, alkoxycarbonyl or NE ⁱ -E ² ', where E ¹ and E ^{2 can be the} same or different and for Are alkyl, cycloalkyl or aryl,

B represents either a carbon-carbon single bond or a divalent bridging group,

or salts and mixtures thereof.

A catalyst according to claim 1, wherein B is a bridging group of the general formulas -D-, - (CO) -D- (CO) - or - (CO) - (CO) -, wherein

D represents a Ci to Cχo alkylene bridge, the one, two, three or four double bonds and / or one, two, three or four substituents selected from alkyl, alkoxy, halogen, nitro, cyano, carboxyl, carboxylate, Can have cycloalkyl and aryl, where the aryl substituent can additionally carry one, two or three substituents which are selected from alkyl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano, and / or the alkylene bridge D can be interrupted by one, two or three non-adjacent, optionally substituted heteroatoms, and / or the alkylene bridge D can be fused one, two or three times with aryl and / or hetaryl, the fused aryl and hetaryl groups each having one, two or three substituents which are selected from alkyl, cycloalkyl, aryl, alkoxy, cycloalkoxy, aryloxy, acyl, halogen, trifluoromethyl, nitro, cyano, carboxyl, alkoxycarbonyl or NE ¹ E ² , can carry, where E ⁱ and E ^{2 may be the} same or different and represent alkyl, cycloalkyl or aryl.

3. Catalyst according to claim 2, wherein D for a radical of the formula II.1, II.2, II.3, II.

4 or II.5

stands in what

represents O, S, NR ⁹ , where

R ^{9 represents} alkyl, cycloalkyl or aryl,

or Y represents a C ₁ -C ₃ -alkylene bridge which can have a double bond and / or an alkyl, cycloalkyl or aryl substituent, the aryl substituent being one, two or three substituents which are selected from alkyl, alkoxy, Halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano,

R ⁱ , R ² 'R ³ ' R ⁴ 'R ⁵ ' R ⁶ 'R ⁷ and R ⁸ independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkoxy, halogen, trifluoromethyl, nitro, alkoxycarbonyl or cyano.

Catalyst according to one of the preceding claims, wherein the phosphinamidite ligand is selected from ligands of the formulas purple to uli

(purple) (Illb) (IIIC)

(Illd) (ine)

(Ulf)

(Illh)

(Uli)

wherein

R ⁹ and R ⁱ ° independently of one another represent hydrogen, methyl, ethyl or trifluoromethyl, R ^{n represents} hydrogen or COOC ₂ H ₅ ,

B represents CH ₂ , C (CH ₃ ) ₂ , (CO) - (CO) or (CO) -D- (CO),

where B in the formulas Illg, Illh and Uli can each be in the 0.0, m, m or p, p positions to the phosphorus atoms, and

D represents a C ~ to Cχo alkylene bridge as defined in one of claims 2 or 3.

5. Catalyst according to one of the preceding claims, characterized in that the metal of subgroup VIII is selected from cobalt, ruthenium, iridium, rhodium, nickel, palladium and platinum.

6. Catalyst according to one of the preceding claims, which additionally at least one further ligand, selected from halides, amines, carboxylates, acetylacetonate, aryl or alkyl sulfonates, hydride, CO, olefins, dienes, cycloolefins, nitriles, N-containing heterocycles, aromatics and Has heteroaromatics, ethers, PF ₃ and monodentate, bidentate and multidentate phosphine, phosphinite, phosphonite and phosphite ligands.

7. A process for the hydroformylation of compounds which contain at least one ethylenically unsaturated double bond by reaction with carbon monoxide and hydrogen in the presence of a hydroformylation catalyst, characterized in that a catalyst according to one of claims 1 to 6 is used as the hydroformylation catalyst.

8. A process for the hydrocyanation of compounds which contain at least one ethylenically unsaturated double bond by reaction with hydrogen cyanide in the presence of a hydrocyanation catalyst, characterized in that a catalyst according to one of claims 1 to 6 is used as the hydrocyanation catalyst.

9. The method according to any one of claims 7 or 8, characterized in that the hydroformylation catalyst or the hydrocyanation catalyst is prepared in situ, wherein at least one phosphinamide ligand as defined in claims 1 to 6, a compound or a complex of a metal of VIII. Subgroup and optionally an activating agent in an inert solvent under the hydroformed mylation conditions or hydrocyanation conditions to react.

10. Use of catalysts comprising a phosphinamidite ligand according to one of claims 1 to 6 for the hydroformylation or hydrocyanation of compounds having at least one ethylenically unsaturated double bond.

10 183 /

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